EP0223448B1 - Lichtempfindliche Elemente - Google Patents

Lichtempfindliche Elemente Download PDF

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Publication number
EP0223448B1
EP0223448B1 EP86308376A EP86308376A EP0223448B1 EP 0223448 B1 EP0223448 B1 EP 0223448B1 EP 86308376 A EP86308376 A EP 86308376A EP 86308376 A EP86308376 A EP 86308376A EP 0223448 B1 EP0223448 B1 EP 0223448B1
Authority
EP
European Patent Office
Prior art keywords
light receiving
atoms
layer
receiving member
support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86308376A
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English (en)
French (fr)
Other versions
EP0223448A3 (en
EP0223448A2 (de
Inventor
Mitsuru Honda
Keeichi Murai
Kyosuke Ogawa
Atsushi Koike
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP23955285A external-priority patent/JPS6299758A/ja
Priority claimed from JP24189285A external-priority patent/JPS62100763A/ja
Priority claimed from JP24157585A external-priority patent/JPS62102249A/ja
Priority claimed from JP24278785A external-priority patent/JPS62103656A/ja
Priority claimed from JP24414385A external-priority patent/JPS62106469A/ja
Application filed by Canon Inc filed Critical Canon Inc
Publication of EP0223448A2 publication Critical patent/EP0223448A2/de
Publication of EP0223448A3 publication Critical patent/EP0223448A3/en
Application granted granted Critical
Publication of EP0223448B1 publication Critical patent/EP0223448B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08235—Silicon-based comprising three or four silicon-based layers
    • G03G5/08242—Silicon-based comprising three or four silicon-based layers at least one with varying composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08221—Silicon-based comprising one or two silicon based layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08221—Silicon-based comprising one or two silicon based layers
    • G03G5/08228—Silicon-based comprising one or two silicon based layers at least one with varying composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
    • G03G5/08214—Silicon-based
    • G03G5/08235—Silicon-based comprising three or four silicon-based layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/10—Bases for charge-receiving or other layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

  • This invention concerns light-receiving members that are sensitive to electromagnetic waves such as light (which includes ultra violet rays, visible rays, infrared rays, X-rays and gamma rays). More specifically the invention relates to improved light-receiving members that are particularly suitable where coherent light e.g. from a laser is used. The invention also concerns the use of the light-receiving member is an electrophotographic process.
  • Light-receiving members that can be imaged by an electrophotographic process using a semiconductor layer comprise amorphous materials containing silicon atoms (hereinafter referred to as "a-Si"), for example as disclosed in Japanese Laid Open Patent Specification Nos. 86341/1979 and 83746/1981. They have a high Vickers hardness, give rise to less problems of environmental pollution and as compared with other known kinds of light-receiving member have photosensitive regions that are an excellent match for the wavelength of the light emitted from the laser source.
  • a-Si amorphous materials containing silicon atoms
  • a light-receiving layer constituting the light-receiving member described above is formed as an a-Si monolayer, it is necessary to incorporate hydrogen or halogen atoms, or further, boron atoms into the layer structure in order to maintain a high photosensitivity together with a dark resistance of greater than 10120 cm.
  • the freedom of design of the light-receiving member has been severely limited by the strict control required of the conditions under which the layer is formed.
  • the light-receiving layer may have two or more layers of different conductivity with a depletion layer formed to the inside of a light-receiving layer as described in Japanese Laid Open Patent Specification Nos. 171743/1979, 4053/1982, 4172/1982.
  • the apparent dark resistance may be improved by providing a multi-layered structure in which a barrier layer is disposed between a support and a light-receiving layer and/or on the upper surface of a light-receiving layer as disclosed for example in Japanese Laid Open Patent Specification Nos. 52178/1982, 52179/1982, 52180/1982, 58159/1982, 58160/1982 and 58161/1982.
  • the individual layers are each of uneven thickness.
  • the free surface and the layer interfaces are collectively referred to as an "interface”.
  • Light reflected at the various interfaces often give rise to interference on fringe pattern in the images formed, resulting in defective images.
  • a light-receiving member of multi-layered structure In a light-receiving member of multi-layered structure, light reflected at each interface can give rise to interference and the respective interferences interact synergistically resulting in an interference fringe pattern which acts directly on the transfer material so that inference fringes on the member become transferred and fixed. Thus there is a visible image corresponding to the interference fringe pattern which gives rise to a defective image. Particularly in the case of intermediate tone images with high gradation, the images obtained become extremely poor in identification.
  • a further problem is that the foregoing interference phenomena become increasingly marked as the wavelength region of the semiconductor laser beams used is increased since the absorption of the laser beams in the light-receiving layer is decreased.
  • Various methods have been proposed in order to overcome these problems, but although they can provide a partial solution, they are not sufficient to eliminate interference fringe patterns from the resulting images.
  • Japanese Laid Open Patent Specification No. 16554/1982 describes providing a light scattering and reflection preventing layer on the surface of aluminium support by treating the surface of the support with a satin-like alumite or by sand blasting the surface of the support to form a fine grain-like unevenness.
  • a portion of the incident light is reflected at the surface of the light-receiving layer, whilst the remainder intruded into the light-receiving layer as transmitted light.
  • part of the transmitted light is scattered as a diffuse light, but the remainder is reflected as a regularly reflected light, part of which appears in the outgoing light.
  • the outgoing light has a component which interferes with the regularly reflected light, and since the component of regularly reflected light cannot be eliminated, the interference fringe pattern also cannot be completely eliminated. It has been attempted to avoid multiple reflections within the light-receiving layer by increasing diffusibility at the surface of the support. However, the result is to increase light diffusion in the light-receiving layer which causes halation and consequently reduces resolving power.
  • a light-receiving member of multi-layered structure if the support surface is irregularly roughened, the reflected light at the surface of the first layer, the reflected light at the second layer and regularly reflected light at the support surface interfere with one another and give rise to an interference fringe pattern depending upon the thickness of each layer in the light-receiving member. Accordingly, in a light-receiving member having a multi-layered structure it is not possible to eliminate interference fringes simply by roughening the surface of the support.
  • the resulting surface roughness varies from one batch to another, and differences in roughness occur even in the same batch, which gives rise to difficulties in production control. Furthermore, relatively large protrusions are frequently and randomly formed, and these large protrusions cause local break-down in the light-receiving layer.
  • the surface of the support has a regular pattern of roughness
  • the light-receiving layer usually follows the shape irregularities at the surface of the support, inclined surfaces on the support due to the unevenness thereof result in parallel inclined surfaces in the light-receiving layer, where the incident light gives rise to bright and dark areas.
  • a pattern of dark and bright stripes occurs in the light-receiving layer because the layer thickness is not uniform over the whole layer. Accordingly, development of an interference fringe pattern cannot be eliminated simply by roughness having a regular pattern on the surface of the support.
  • the present invention provides a light-receiving member for exposure to light to form an image, which member comprises a support and a light receiving layer of multi-layered structure formed thereon, said light receiving layer comprising an inner photosensitive layer composed of an amorphous material containing silicon atoms and at least either germanium atoms or tin atoms and an outer photosensitive layer composed of an amorphous material containing silicon atoms and neither germanium atoms nor tin atoms, said support having a surface provided with a plurality of spherical dimples distributed over the surface in such a way that their perimeters are in contact, wherein the radius of curvature R and the width D of the spherical dimples have values satisfying the criterion: 0.035 # D/R ⁇ 0.5, with 0.5 mm and each of said dimples has an inside face provided with minute irregularities each having a height h which satisfies the criterion: 0.5 pm Z h :-5 20 pm.
  • the above light receiving member may comprise a light receiving layer comprising a-Si in which the electrical, optical and photoconductive properties are substantially stable and independent of working circumstances.
  • the member may be resistant to optical fatigue, and may give rise to no degradation upon repeated use, may be durable and moisture-proof, may exhibit little or no residual potential and may provide for easy production control.
  • the light receiving layer composed of a-Si may exhibit a high photosensitivity in the entire visible region of light, particularly, an excellent matching property with a semiconductor laser, and may exhibit a quick light response, high photosensitivity, high S/N ratio, and high resistance to electrical voltage.
  • the a-Si layer may further exhibit close bondability to the support and the layer disposed on the support or between the laminated layers, may have a well-defined and stable structural arrangement and may be of high layer quality. It may be suitable for the image formation using coherent light, may be free from the occurrence of interference fringe patterns and spots upon reversed development even after repeated use for a long period of time, may be free from defective images or blurring in the images, may show high density with clear half tone, may have high resolving power, and may provide high quality images.
  • the present inventors made earnest studies for overcoming the foregoing problems on the conventional light receiving members and attaining the objects as described above and, as a result, obtained the following findings, and have completed this invention based on those findings.
  • a light receiving layer composed of a-Si when incorporated with germanium atoms and/or tion atoms, it becomes more sensitive to light of wavelengths broadly ranging from short wavelength to long wavelength covering visible light and it also becomes quickly responsive to light. This effect is pronounced when the light receiving layer is of double-layered structure in which the layer adjacent to the support contains germanium atoms and/or tin atoms and the layer facing outward contains neither germanium atoms nor tin atoms.
  • the light receiving layer of such structure is useful in instances where a semiconductor laser is used as the light source of long wavelength, because the lower layer containing germanium atoms and/or tin atoms substantially completely absorbs the light which the upper layer containing neither germanium atoms nor tin atoms can absorb very little. This light absorption prevents the interference resulting from the light reflected by the surface of the support.
  • the light receiving member having a plurality of layers as mentioned above significantly prevent the occurrence of the interference fringe pattern, whcih often occurs upon image formation in a conventional light receiving member, when the surface of the support is provided with irregularities composed of a plurality of spherical dimples each of which having an inside face provided with minute irregularities.
  • FIGS 1(A) and 1(B) are schematic views respectively illustrating the layer structure of the light receiving member 100 pertaining to this invention.
  • the light receiving member is made up of a support 101 and a light receiving layers 102 formed thereon.
  • the support 101 has irregularities composed of a plurality of fine spherical dimples each of which having an inside face provided with minute irregularities at the surface thereof.
  • the light receiving layer 102 is formed along the slopes of the irregularities, and is constituted by a layer 102' containing silicon atoms and at least either of germanium atoms or tion atoms and a layer 102" containing silicon atoms but containing neither germanium atoms nor tin atoms.
  • Figure 1 (A) is a schematic view for illustrating a typical layer structure of the light receiving member of this invention, in which are shown the light receiving member 100, the support 101, the light receiving layer 102, the layer 102' containing at least either germanium atoms or tin atoms, the layer 102" containing neither germanium atoms nor tin atoms, and a free surface 104.
  • Figure 1 (B) is a schematic view for illustrating another typical layer structure of the light receiving member of this invention, in which are shown the light receiving member 100, the support 101, the light receiving layer, the layer 102' containing at least either germanium atoms or tin atoms, the layer 102" containing neither germanium atoms nor tin atoms, a surface layer 103 and a free surface 104.
  • Figures 2 and 3 are views explaining how the problem of interference fringe pattern is solved in the light receiving member of this invention.
  • Figure 3 is an enlarged view for a portion of a conventional light receiving member in which a light receiving layer of a multi-layered structure is deposited on the support the surface of which is regularly roughened.
  • a first layer 301, a second layer 302, a free surface 303, and an interface 304 between the first and second layers are shown.
  • the light receiving layer is usually formed along the uneven shape at the surface of the support, the slope of the unevenness at the surface of the support and the slope of the unevenness of the light receiving layer are in parallel with each other.
  • the following problems always occur, for example, in a light receiving member of multi-layered structure in which the light receiving layer comprises two layers, that is, a first layer 301 and the second layer 302. Since the interface 304 between the first layer and the second layer is in parallel wioth the free surface 303, the direction of the reflected light R 3 at the interface 304 and that of the reflected light R 4 at the free surface coincides with each other and, accordingly, an interference fringe occurs depending on the thickness of the second layer.
  • Figure 2 is an enlarged view for a portion of the light receiving member according to this invention as shown in Figure 1(A) or Figure 1 (B), in which a light receiving layer of multi-layered structure is deposited on an unevenly shaped surface composed of a plurality of fine spherical dimples each of which having an inside face provided with minute irregularities.
  • a light receiving layer of multi-layered structure is deposited on an unevenly shaped surface composed of a plurality of fine spherical dimples each of which having an inside face provided with minute irregularities.
  • an uneven shape composed of a plurality of the fine spherical dimples are formed at the surface of the support in the light receiving member according to this invention, and the light receiving layer thereover is deposited along the uneven shape.
  • the interface 204 between the first layer 201 and the second layer 202, and the free surface 203 are respectively formed with the uneven shape composed of the spherical dimples along the uneven shape at the surface of the support.
  • the reflection light at the interface 204 and the reflection light at the free surface 203 have reflection angles different from each other, that is, 0 1 is not identical with 6 2 in Figure 2 and the direction of their reflection lights are differnt.
  • the deviation of the wavelength represented by I 1 + 1 2 - 1 3 by using I 1 , 1 2 and 1 3 shown in Figures 2 is not constant but variable, by which a sharing interference corresponding to the so-called Newton ring phenomenon occurs and the interference fringe is dispersed within the dimples. Then, if the interference ring should appear in the microscopic point of view in the images caused by way of the light receiving member, it is not visually recognized.
  • the fringe pattern resulted in the images due to the interference between lights passing through the light receiving layer and reflecting on the layer interface and at the surface of the support thereby enabling to obtain a light receiving member capable of forming excellent images.
  • the radius of curvature R and the width D of the uneven shape formed by the spherical dimples, at the surface of the support of the light receiving member according to this invention constitute an important factor for effectively attaining the advantageous effect of preventing the occurrence of the interference fringe in the light receiving member according to this invention.
  • the present inventors carried out various experiments and, as a result, found the following facts.
  • the radius of curvature R and the width D satisfy the following equation: 0.5 or more Newton rings due to the sharing interference are present in each of the dimples. Further, if they satisfy the following equation: one or more Newton rings due to the sharing interference are present in each of the dimples.
  • the ratio D/R is greater than 0.035 and, preferably, greater than 0.055 for dispersing the interference fringes resulted throughout the light receiving member in each of the dimples thereby preventing the occurrence of the interference fringe in the light receiving member.
  • the width D of the unevenness formed by the scraped dimple is about 500 pm at the maximum preferably, less than 200 pm and, more preferably less than 100 pm.
  • the height of the minute irregularity to be provided with the inside face of the spherical dimple of the support namely the surface roughness Y max of the inside face of the spherical dimple lies in the range of 0.5 to 20 pm.
  • the present invention has been completed on the basis of the above-mentioned findings.
  • a light receiving member which comprises a support and a light receiving layer of multi-layered structure formed thereon, said light receiving layer being composed of an inner layer of amorphous material containing silicon atoms and at least either germanium atoms or tin atoms and an outer layer of amorphous material containing silicon atoms and neither germanium atoms nor tin atoms, said support having a surface provided with irregularities composed of spherical dimples each of which having an inside face provided with minute irregularities.
  • Another aspect of the invention resides in a light receiving member as stipulated above, wherein the light receiving layer contains at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms.
  • a light receiving member as mentioned above, which further comprises a surface layer which is formed on said light receiving layer and is made of an amorphous material containing silicon atoms and those atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms which are different from those atoms contained in the said light receiving layer.
  • Still further another aspect of the invention resides in a light receiving member as mentioned above, which further comprises a surface layer which is formed on said light receiving layer and has the function of preventing reflection.
  • Figures 1 (A) is a schematic view for illustrating the typical layer structure of the light receiving member of this invention, in which are shown the light receiving member 100, the support 101, the light receiving layer 102, the layer 102' containing at least either germanium atoms or tin atoms, the layer 102" containing neither germanium atoms not tin atoms, and the free surface 103. Explanation will be made for the support 101 and the light receiving layer 102.
  • the support 101 in the light receiving member according to this invention has a surface with fine unevenness smaller than the resolution power required for the light receiving member and the unevenness is composed of a plurality of spherical dimples each of which having an inside face provided with minute irregularities.
  • Figure 4 is a schematic view for a typical example of the shape at the surface of the support in the light receiving member according to this invention, in which a portion of the uneven shape is enlarged.
  • FIG 4 are shown a support 401, a support surface 402, an irregular shape due to a spherical dimple (spherical cavity pit) 403, an inside face of the spherical dimple 404 which is provided with minute irregularities and a rigid sphere 403' having a surface 404' which is provided with minute irregularities.
  • a spherical dimple spherical cavity pit
  • Figure 4 also shows an example of the preferred methods of preparing the surface shape of the support.
  • the rigid sphere 403' is caused to fall from a position at a predetermined height above the support surface 402 and collides against the support surface 402 whereby forming the spherical dimple 403 having the inside face provided with minute irregularities 404.
  • a plurality of the spherical dimples each substantially of an almost identical radius of curavture R and of an almost identical width D can be formed to the support surface 402 by causing a plurality of the rigid spheres 403' substantially of an identical diameter of curvature R' to fall from identical height h simultaneously or sequentially.
  • Figures 5(A) through 5(C) show typical embodiments of supports formed with the uneven shape composed of a plurality of spherical dimples each of which has an inside face provided with minute irregularities at the support surface as described above.
  • FIGS 5(A) through 5(C) are shown a support 501, a support surface 502, a spherical dimple (spherical cavity pit) having an inside face provided with minute irregularities (not shown) 504 or 504' and a rigid sphere of which surface has minute irregularities (not shown) 503 or 503'.
  • a plurality of the dimples (spherical cavity pits) 503, 503, ... of an almost identical radius of curvature and of an almost identical width are formed while being closely overlapped with each other thereby forming an uneven shape regularly by causing to fall a plurality of spheres 503', 503', ... regularly from an identical height to different positions at the support surface 502 of the support 501.
  • a plurality of dimples 504, 504',... having two kinds of diameter of curvature and two kinds of width are formed being densely overlapped with each other to the surface 502 of the support 501 thereby forming an unevenness with irregular height at the surface by dropping two kinds of spheres 503, 503', ... of different diameters from the heights identical with or different from each other.
  • a plurality of dimples 504, 504, ... of an almost identical diameter of curvature and plural kinds of width are formed while being overlapped with each other thereby forming an irregular unevenness by causing to fall a plurality of spheres 503, 503,... of an identical diameter from the identical height irregularly to surface 502 of the support 501.
  • the uneven shape of the support surface composed of the spherical dimples each of which having an inside face provided with irregularities can be formed preferably by dropping the rigid spheres repectively of a surface provided with minute irregularities to the support surface.
  • a plurality of spherical dimples having desired radius of curvature and width can be formed at a predetermined density on the support surface by properly selecting various conditions such as the diameter of the rigid spheres, falling height, hardness for the rigid sphere and the support surface or the amount of the fallen spheres. That is, the height and the pitch of the uneven shape formed for the support surface can optionally be adjusted depending on the given purpose by selecting various conditions as described above thereby enabling to obtain a support having a desired uneven shape with the support surface.
  • the support 101 for use in this invention may either be electroconductive or insulative.
  • the electroconductive support can include, for example, metals such as NiCr, stainless steel, Al, Cr, Mo, Au, Nb, Ta, V, Ti, Pt, and Pb, or the alloys thereof.
  • the electrically insulative support can include, for example, film or sheet of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polyamide; glass, ceramics, and paper. It is preferred that the electrically insulative support is applied with electro-conductive treatment to at least one of the surfaces thereof and disposed with a light receiving layer on the thus treated surface.
  • electroconductivity is applied by disposing, at the surface thereof, a thin film made of NiCr, Al, Cr, Mo, Au, lr, Nb, Ta, V, Ti, Pt, Pd, ln 2 0 2 , Sn0 3 , ITO (ln 3 O 3 + Sn0 2 ), etc.
  • the electroconductivity is provided to the surface by disposing a thin film of metal such as NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, TI, and Pt by means of vacuum deposition, electron beam vapor deposition, sputtering, etc.
  • the support may be of any configuration such as cylindrical, belt-like or platelike shape, which can be properly determined depending on the applications.
  • the thickness of the support member is properly determined so that the light receiving member as desired can be formed. In the case where flexibility is required for the light receiving member, it can be made as thin as possible within a range capable of sufficiently providing the function as the support. However, the thickness is usually greater than 10 11m in view of the fabrication and handling or mechanical strength of the support.
  • a cylindrical substrate is prepared as a drawn tube obtained by applying usual extruding work to aluminum alloy or the like other material into a boat hall tube or a mandrel tube and further applying drawing work, followed by optical heat treatment or tempering. Then, an uneven shape is formed at the surface of the support at the cylindrical substrate by using the fabrication device as shown in Figures 6(A) and 6(B).
  • the rigid sphere to be used for forming the uneven shape as described above on the support surface can include, for example, various kinds of rigid spheres made of stainless steel, aluminum, steel, nickel, and brass, and like other metals, ceramics and plastics. Among all, rigid spheres of stainless steel or steel are preferred in view of the durability and the reduced cost. The hardness of such sphere may be higher or lower than that of the support. However, in the case of using the rigid spheres repeatedly, it is desired that the hardness of sphere is higher than that of the support.
  • Such rigid spheres may be prepared properly in accordance with a mechanical treatment method such as a method utilizing plastic processing treatment such as embossing and wave adding and a surface roughing method such as sating finishing, or a chemical treatment method such as acid etching or alkali etching.
  • a mechanical treatment method such as a method utilizing plastic processing treatment such as embossing and wave adding and a surface roughing method such as sating finishing, or a chemical treatment method such as acid etching or alkali etching.
  • the shape (height) orthe hardness of the irregularities as formed on the surface of the rigid sphere may be adjusted properly by subjecting the rigid sphere to the surface treatment in accordance with electropolishing, chemical polishing or finish polishing, or anodic oxidation coating, chemical coating, planting, vitreous enameling, painting, evaporation film forming or CVD film forming.
  • Figures 6(A) and 6(B) are schematic cross-sectional views for the entire fabrication device, in which are shown an aluminum cylinder 601 for preparing a support, and the cylinder 601 may previously be finished at the surface to an appropriate smoothness.
  • the cylinder 601 is supported by a rotating shaft 602, driven by an appropriate drive means 603 such as a motor and made rotatable around the axial center. The rotating speed is properly determined and controlled while considering the density of the spherical dimples to be formed and the amount of rigid spheres supplied.
  • a rotating vessel 604 is supported by the rotating shaft 602 and rotates in the same direction as the cylinder 601 does.
  • the rotating vessel 604 contains a plurality of rigid spheres each of which having a surface provided with minute irregularities 605, 605, ...
  • the rigid spheres are held by plural projected ribs 606, 606, ... being disposed on the inner wall of the rotating vessel 604 and transported to the upper position by the rotating action of the rotating vessel 604.
  • the rigid spheres 605, 605, ... then continuously fall down and collide against the surface of the cylinder 601 thereby forming a plurality of spherical dimples each of which having an inside face provided with irregularities when the revolution speed of the rotating vessel 604 is maintained at an appropriate rate.
  • the fabrication device can be structured in the following way. That is, the circumferential wall of the rotating vessel 604 are uniformly perforated so as to allow the passage of a washing liquid to be jetting-like supplied from one or more of a showering pipe 607 being placed outside the rotating vessel 604 thereby having the cylinder 601, the rigid spheres 605, 605, ... and also the inside of the rotating vessel 604 washed with the washing liquid.
  • washing liquid it is necessary to use such that does not give any dry unevenness or any residue.
  • a washing liquid such as trichloroethane or trichloroethylene are preferable.
  • the light receiving layer 102 is formed on the above-mentioned support 101.
  • the light receiving layer is of multi-layered structure composed of the layer 102' adjacent to the support 101 and the layer 102" formed on the layer 102'.
  • the layer 102' is made of a-Si containing at least either germanium atoms (Ge) or tin atoms (Sn) and preferably at least either hydrogen atoms or halogen atoms. (This a-Si is referred to as a-Si(Ge,Sn) (H,X) hereinafter.)
  • the layer 102" is made of a-Si which, if necessary, contains at least either hydrogen atoms or halogen atoms. (This a-Si is referred to as a-Si (H,X) hereinafter.)
  • the halogen atom (X) contained in the light receiving layer include, specifically, fluorine, chlorine, bromine, and iodine, fluorine and chlorine being particularly preferred.
  • the amount of the hydrogen atoms (H), the amount of the halogen atoms (X) or the sum of the amounts of the hydrogen atoms and the halogen atoms (H+X) contained in the light receiving layer 102 is usually from 1 to 40 atomic% and, preferably, from 5 to 31 atomic%.
  • the thickness of the light receiving layer is one of the important factors for effectively attaining the purpose of this invention and a sufficient care should be taken therefore upon designing the light receiving member so as to provide the member with desired performance.
  • the layer thickness is usually from 1 to 100 um, preferably from 1 to 80 11 m and, more preferably, from 2 to 50 pm.
  • the light receiving layer on the light receiving member of the invention is formed such that the layer 102' adjacent to the support 101 contains germanium atoms and/or tin atoms uniformly distributed therein or unevenly distributed therein.
  • the uniform distribution means that the distribution of germanium atoms and/or tin atoms in the layer 102' is uniform both in the direction parallel with the surface of the support and in the thickness direction.
  • the uneven distribution means that the distribution of germanium atoms and/or tin atoms in the layer 102' is uniform in the direction parallel with the surface of the support but is uneven in the thickness direction.) In the latter case, it is desirable that germanium atoms and/or tin atoms in the layer 102' be present more in the side adjacent to the support than in the side adjacent to the layer 102". It is especially desirable that the distribution of germanium atoms and/or tin atoms be maximum at the interface in contact with the support. Such constitution is desirable in cases where the light source is a semiconductor laser emitting rays of long wavelengths, because the layer 102' substantially completely absorbs the light of long wavelength the layer 102" hardly absorbs. This prevents the interference caused by the light reflected by the surface of the support.
  • the abscissa represents the distribution concentration C of germanium atoms and the ordinate represents the thickness of the layer 102'; and t B represents the extreme position of the layer 102' adjacent to the support and t T represent the other extreme position adjacent to the layer 102" which is away from the support.
  • the layer 102' containing germanium atoms is formed from the t B side toward the t T side.
  • Figure 7 shows the first typical example of the thicknesswise distribution of germanium atoms in the layer 102'.
  • germanium atoms are distributed such that the concentration C is constant at a value C 1 in the range from position t B (at which the layer 102' containing germanium atoms is in contact with the surface of the support) to position t 1 , and the concentration C gradually and continuously decreases from C 2 in the range from position t 1 to position t T at the interface.
  • the concentration of germanium atoms is substantially zero at the interface position t T .
  • Substantially zero means that the concentration is lower than the detectable limit.
  • the distribution of germanium atoms contained is such that concentration C 3 at position t B gradually and continuously decreases to concentration C 4 at position t T .
  • the distribution of germanium atoms is such that concentration C 5 is constant in the range from position t B and position t 2 and it gradually and continuously decreases in the range from position t 2 to position t T .
  • concentration at position t T is substantially zero.
  • the distribution of germanium atoms is such that concentration C 6 gradually and continuously decreases in the range from position t B and position t 3 , and it sharply and continuously decreases in the range from position t 3 to position t T .
  • the concentration at position t T is substantially zero.
  • the distribution of germanium atoms is such that concentration C 7 is constant in the range from position t B and position t 4 and it linearly decreases in the range from position t 4 to position t T .
  • concentration at position t T is zero.
  • the distribution of germanium atoms is such that concentration C 8 is constant in the range from position t B and position t 5 and concentration Cg linearly decreases to concentration C 10 in range from position t s to position t T .
  • the distribution of germanium atoms is such that concentration linearly decreases to zero in the range from position t B to position t T .
  • the distribution of germanium atoms is such that concentration C 12 linearly decreases to C 13 in the range from position t B to position t 6 and concentration C 13 remains constant in the range from position t 6 to position t T .
  • the distribution of germanium atoms is such that concentration C 14 at position t B slowly decreases and then sharply decreases to concentration C 15 in the range from position t B to position t 7 .
  • the concentration sharply decreases at first and slowly decreases to C, 6 at position t 8 .
  • the concentration slowly decreases to C 17 between position t 8 and position tg.
  • Concentration C 17 further decreases to substantially zero between position tg and position t T .
  • the concentration decreases as shown by the curve.
  • the concentration of germanium atoms and/or tin atoms in the layer 102' should preferably be high at the position adjacent to the support and considerably low at the position adjacent to the interface t T .
  • the layer 102' constituting the light receiving member of this invention have a region adjacent to the support in which germanium atoms and/or tin atoms are locally contained at a comparatively high concentration.
  • Such a local region in the light receiving member of this invention should preferably be formed within 5 pm from the interface t 8 .
  • the local region may occupy entirely or partly the thickness of 5 ⁇ m from the interface position t B .
  • the local region should occupy entirely or partly the layer 102' depends on the performance required for the light receiving layer to be formed.
  • the thicknesswise distribution of germanium atoms and/or tin atoms contained in the local region should be such that the maximum concentration C max of germanium atoms and/or tin atoms is greater than 1000 atomic ppm, preferably greater than 5000 atomic ppm, and more preferably greater than 1 x 10 4 atomic ppm based on the amount of silicon atoms.
  • the layer 102' which contains germanium atoms and/or tin atoms should preferably be formed such that the maximum concentration C max of their distribution exists within 5 pm of thickness from t e (or from the support side).
  • the amount of germanium atoms and/or tin atoms in the layer 102' should be properly determined so that the object of the invention is effectively achieved. It is usually 1 to 6 x 10 s atomic ppm, preferably 10 to 3 x 10 s atomic ppm, and more preferably 1 x 10 2 to 2 x 10 1 atomic ppm.
  • a substance for controlling the electroconductivity may be contained to the light receiving layer in a uniformly or unevenly distributed state to the entire or partial layer region.
  • impurities in the field of the semiconductor can include atoms belonging to the group III of the periodic table that provide p-type conductivity (hereinafter simply referred to as "group III atoms") or atoms belonging to the group V of the periodic table that provide n-type conductivity (hereinafter simply referred to as "group V atoms").
  • group III atoms can includer B (boron), AI (aluminum), Ga (gallium), In (indium), and TI (thallium), B and Ga being particularly preferred.
  • the group V atoms can include, for example, P (phosphorus), As arsenic), Sb (antimony), and Bi (bismuth), P and Sb being particularly preferred.
  • the group III or group V atoms as the substance for controlling the conductivity into the light receiving layer of the light receiving member according to this invention, they are contained in the entire layer region or partial layer region depending on the purpose or the expected effects as described below and the content is also varied.
  • the substance is contained in the entire layer region of the photosensitive layer, in which the content of group III or group V atoms may be relatively small and it is usually from 1 x 10- 3 to 1 x 10 3 atomic ppm, preferably from 5 x 10- 2 to 5 x 10 2 atomic ppm, and most suitably, from 1 x 10 -1 to 5 x 10 2 atomic ppm.
  • the constituting layer containing such group III or group V atoms or the layer region containing the group III or group V atoms at high concentration functions as a charge injection inhibition layer. That is, in the case of incorporating the group III atoms, movement of electrons injected from the side of the support into the light receiving layer can effectively be inhibited upon applying the charging treatment of at positive polarity at the free surface of the light receiving layer.
  • the content in this case is relatively great. Specifically, it is generally from 30 to 5 x 10' atomic ppm, preferably from 50 to 1 x 10 4 atomic ppm, and most suitably from 1 x 10 2 to 5 x 10 3 atomic ppm.
  • the thickness (T) of the light receiving layer and the thickness (t) of the layer or layer region containing the group III or group V atoms adjacent to the support should be determined such that the relation t/T ⁇ 0.4 is established. More preferably, the value for the relationship is less than 0.35 and, most suitably, less than 0.3. Further, the thickness (t) of the layer or layer region is generally 3 x 10- 3 to 10 pm, preferably 4 x 10- 3 to 8 ⁇ m, and, most suitably, 5 x 10- 3 to 5 pm.
  • the abscissa represents the distribution concentration C of the group III atoms or group V atoms and the ordinate represents the thickness of the light receiving layer; and t B represents the interface position between the support and the light receiving layer and t T represents the position of the free surface of the light receiving layer.
  • the layer 102' containing germanium atoms is formed from the t B side toward the t T side.
  • Figure 16 shows the first typical example of the thicknesswise distribution of the group III atoms or group V atoms in the light receiving layer.
  • the group III atoms or group V atoms are distributed such that the concentration C remains constant at a value C, in the range from position t e (at which the light receiving layer comes into contact with the support) to position t 1 , and the concentration C gradually and continuously decreases from C 2 in the range from position t, to position t T , where the concentration of the group III atoms or group V atoms is C 3 .
  • the distribution concentration C of the group III atoms or group V atoms contained in the light receiving layer is such that concentration C 4 at position t B continuously decreases to concentration C 5 at position t T .
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 6 remains constant in the range from position t e to position t 2 and it gradually and continuously decreases in the range from position t 2 to position t T .
  • the concentration at position t T is substantially zero.
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 8 gradually and continuously decreases in the range from position t B to position t T , at which it is substantially zero.
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 9 remains constant in the range from position t B to position t 3 , and concentration C 8 linearly decreases to concentration C 10 in the range from position t 3 to position t T .
  • the distribution concentration C of the group lll atoms or group V atoms is such that concentration C 11 remains constant in the range from position t B to position t 4 and it linearly decreases from C 12 to C 13 in the range from position t 4 to position t T .
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 14 linearly decreases in the range from position t B to position t T , at which the concentration is substantially zero.
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 15 linearly decreases to concentration C 16 in the range from position t B to position t 5 and concentration C 16 remains constant in the range from position t 5 to position t T .
  • the distribution concentration C of the group III atoms or group V atoms is such that concentration C 17 a position t B slowly decreases and then sharply decreases to concentration C 18 in the range from position t B to position t 6 .
  • the concentration sharply decreases at first and slowly decreases to C 19 at position t 7 .
  • the concentration slowly decreases between position t 7 and position t e , at which the concentration is C 20 .
  • Concentration C 20 slowly decreases to substantially zero between position t 8 and position t T .
  • the foregoing effect that the layer region where the group III or group V atoms are distributed at a higher concentration can form the charge injection inhibition layer as described above more effectively, by disposing a localized region where the distribution concentration of the group III or group V atoms is relatively higher at the portion near the side of the support, preferably, by disposing the localized region at a position within 5 ⁇ m from the interface position adjacent to the support surface.
  • the distribution state of the group III or group V atoms and the amount of the group III or group V atoms are, of course, combined properly as required for obtaining the light receiving member having performance capable of attaining a desired purpose.
  • a substance for controlling the conductivity of a polarity different from that of the substance for controlling the conductivity contained in the charge injection inhibition layer may be contained in the light receiving layer other than the charge injection inhibition layer, or a substance for controlling the conductivity of the same polarity may be contained by an amount substantially smaller than that contained in the charge inhibition layer.
  • the so-called barrier layer composed of electrically insulating material may be disposed instead of the charge injection inhibition layer as the constituent layer disposed at the end on the side of the support, or both of the barrier layer and the charge injection inhibition layer may be disposed as the constituent layer.
  • the material for constituting the barrier layer can include, for example, those inorganic electrically insulating materials such as AI 2 0 3 , Si0 2 , and Si 3 N 4 , or organic electrically insulating material such as polycarbonate.
  • the photosensitive layer of the light receiving member of this invention may be incorporated with at least one kind selected from oxygen atoms, carbon atoms, nitrogen atoms. This is effective in increasing the photosensitivity and dark resistance of the light receiving member and also in improving adhesion between the support and the light receiving layer.
  • the light receiving layer of the invention In the case of incorporating at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms into the light receiving layer of the invention, it is performed at a uniform distribution or uneven distribution in the direction of the layer thickness depending on the purpose or the expected effects as described above, and accordingly, the content is varied depending on them.
  • the dark resistance of the light receiving member they are contained at a uniform distribution over the entire layer region of the light receiving layer.
  • the amount of at least one kind selected from carbon atoms, oxygen atoms, and nitrogen atoms contained in the light receiving layer may be relatively small.
  • At least one kind selected from carbon atoms, oxygen atoms, and nitrogen atoms is contained uniformly in the layer 102' constituting the light receiving layer adjacent to the support, or at least one kind selected from carbon atoms, oxygen atoms, and nitrogen atoms is contained such that the distribution concentration is higher at the end of the light receiving layer on the side of the support.
  • the amount of at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms is comparatively large in order to improve the adhesion to the support.
  • the amount of at least one kind selected form oxygen atoms, carbon atoms, and nitrogen atoms contained in the light receiving layer of the light receiving member according to this invention is also determined while considering the organic relationship such as the performance at the interface in contact with the support, in addition to the performance required for the light receiving layer as described above and it is usually from 0.001 to 50 atomic%, preferably, from 0.002 to 40 atomic%, and, most suitably, from 0.003 to 30 atomic%.
  • the upper limit for the content is made smaller. That is, if the thickness of the layer region incorporated with the element is 2/5 of the thickness for the light receiving layer, the content is usually less than 30 atomic%, preferably, less than 20 atomic% and, more suitably, less than 10 atomic%.
  • the distribution concentration C of at least one kind selected from oxygen atoms, carbon atoms, and nitrogen atoms (referred to as "the atoms (O, C, N)" hereinafter) is higher at the end of the free surface of the light receiving layer on the side of the support, while the distribution concentration C is considerably lower or substantially equal to zero at the end of the first layer on the side of the free surface, improvement in adhesion between the support and the light receiving layer can be attained more effectively by disposing a localized region at the end of the light receiving layer on the side of the support where the distribution concentration of the atoms (0, C, N) is relatively higher and, preferably, by disposing the localized region at a position within 5 pm from the interface position t B between the support surface and the light receiving layer.
  • the localized region may be disposed partially or entirely at the end of the light receiving layer to be contained with the atoms (0, C, N) on the side of the support, which may be properly determined in accordance with the performance required for the light receiving layer to be formed.
  • the amount of the atoms (O, C, N) contained in the localized region is such that the maximum value of the distribution concentration C of the atoms (0, C, N) is greater than 500 atomic ppm, preferably, greater than 800 atomic ppm, most suitably greater than 1000 atomic ppm in the distribution.
  • Figure 1 (B) is a schematic view for illustrating the structure of another layer of the light receiving member of this invention, in which are shown the light receiving member 100, the support 101, the light receiving layer, the layer 102' containing at least either germanium atoms or tin atoms, the layer 102" containing neither germanium atoms nor tin atoms, the free surface 103, and the surface layer 104.
  • the light receiving member shown in Figure 1(B) differs from the above-mentioned light receiving member shown in Figure 1 (A) in that the former has the surface layer 104 as the top layer.
  • An explanation will be made of the surface layer 104 in the following.
  • the surface layer 104 is generally grouped into the following two types.
  • One of them is composed of amorphous silicon [a-Si (0, C, N)(H, X)] containing at least one member selected from oxygen atoms, carbon atoms, and nitrogen atoms, or containing uniformly the atoms different from the member selected from oxygen atoms, carbon atoms, and nitrogen atoms, in the case where the previously formed light receiving layer (i.e., the layer 102' and 102" shown in Figure 1(B)) contains at least one member selected from oxygen atoms, carbon atoms, and nitrogen atoms.
  • amorphous silicon a-Si (0, C, N)(H, X)
  • the surface layer 104 is disposed to the light receiving layer according to this invention with the aim of improving the moisture-proofness, performance for continuous repeating use, electrical voltage withstanding property, circumstantial resistance property, and durability, and these purposes can be attained by incorporating at least one member selected from oxygen atoms, carbon atoms, and nitrogen atoms into the amorphous material constituting the surface layer.
  • each of the amorphous layers constituting the surface layer 104 and the light receiving layer thereunder contains common constituent atoms of silicon, the chemical stability can be ensured at the interface between the surface layer 104 and the light receiving layer thereunder.
  • Atoms selected from oxygen atoms, carbon atoms, and nitrogen atoms are uniformly contained in the surface layer 104, by which the foregoing various properties can be improved in accordance with the increase in the content of these atoms. However, if the content is excessive, the layer quality is reduced and electrical and mechanical properties are also degraded. In view of the above, the amount of these atoms is usually from 0.001 to 90 atomic%, preferably, from 1 to 90 atomic%, and most suitably, from 10 to 80 atomic%.
  • hydrogen atoms or halogen atoms are also contained in the surface layer and the amount of the hydrogen atoms(H), the amount of the halogen atoms(X), or the sum of the amounts for the hydrogen and halogen atoms (H + X) contained in the surface layer is usually from 1 to 40 atomic%, preferably, from 50 to 30 atomic%, and most suitably, from 5 to 25 atomic%.
  • the surface layer has to be formed with an utmost care so as to obtain the properties as desired. That is, the state of the substance comprising silicon atoms, at least one kind of oxygen atoms, carbon atoms, and nitrogen atoms, and, further, hydrogen atoms and/or halogen atoms as the constituent atoms is from crystalline to amorphous state, the electrical property of the layer may vary from the conductive, to semiconductivity and insulating property and, further, the photoelectronic property of the layer may also vary from photoconductive to non-photoconductive property depending on the content of each of the constituent atoms and other conditions of preparation. Accordingly, it is essential to select the content for each of the constituent atoms and the preparation conditions such that the surface layer having desired properties depending on the purpose can be formed.
  • the amorphous material constituting the surface layer is formed such that it exhibits remarkable electrically insulating behavior under the working conditions.
  • the amorphous layer constituting the surface layer is formed such that the layer has photosensitivity to some extent to the irradiated light, although the degree of the electrically insulating property is somewhat moderate.
  • the thickness of the surface layer is also one of the important factors for effectively attaining the purpose of this invention and it is properly determined depending on the desired purposed. It is, however, also necessary that the layer thickness is determined in view of relative and organic relationships in accordance with the amounts of the oxygen atoms, carbon atoms, nitrogen atoms, halogen atoms, and hydrogen atoms contained in the layer or the properties required for the surface layer. Further, it should be determined also in economical point of view such as productivity or mass productivity. In view of the above, the thickness of the surface layer is usually from 3 x 10- 3 to 30 pm, preferably from 4 x 10- 3 to 20 pm, most suitably, from 5 x 10- 3 to 10 pm.
  • the second type of the surface layer 104 provides a function of reducing the reflection and increasing the transmission rate at the free surface 103 of the light receiving layer, that is, the reflection preventive function, as well as the function of improving various properties such as the moisture-proofness, the property for continuous repeating use, electrical voltage withstanding property, circumstantial resistance and durability of the light receiving layer.
  • the material for forming the surface layer is required to satisfy various conditions in that it can provide the excellent reflection preventive function for the layer constituted therewith, and a function of improving the various properties as described above, as well as those conditions in that it does not give undesired effects on the photoconductivity of the light receiving member, provides an adequate electronic photographic property, for example, an electric resistance over a certain level, provide an excellent solvent resistance in the case of using the liquid developing process and it does not reduce the various properties of the light receiving layer already formed.
  • Those materials that can satisfy such various conditions and can be used effectively include, for example, at least one of materials selected from inorganic fluorides, inorganic oxides, and inorganic sulfides such as MgF 2 AI 2 0 3 , Zr0 2 , Ti0 2 , ZnS, Ce0 2 , CeF 3 , Ta 2 0 5 , AIF 3 and NaF.
  • n represents the refractive index of the material for forming the surface layer
  • n a represents the refractive index of the layer constituting the layer laminated directly to the surface layer
  • refractive indexes of inorganic fluorides, inorganic oxides, and inorganic sulfides, or the mixtures thereof as described above will now be referred to.
  • the refractive index is varied somewhat depending on the kinds of the layer to be prepared, conditions, and the like. Numerical values in the parentheses represent the refractive index.
  • the thickness d of the surface layer can satisfy the conditions expressed by the following equation: where d represents the thickness of the surface layer, n represents the refractive index of the material constituting the surface layer, and A represents the wavelength of the irradiated light. Specifically, in the case where the wavelength of the exposing light is within the wavelength range from the near infrared to the visible rays, the thickness d of the surface layer is preferably defined as from 0.05 to 2 um.
  • the light receiving member according to this invention has a high photosensitivity in the entire visible ray region and, further, since it is excellent in the photosensitive property on the side of the longer wavelength, it is suitable for the matching property, particularly, with a semiconductor laser, exhibits a rapid optical response and shows more excellent electrical, optical and electroconductive nature, electrical voltage withstand property and resistance to working circumstances.
  • the light receiving member in the case of applying the light receiving member to the electrophotography, it gives no undesired effects at all of the residual potential to the image formation, stable electrical properties high sensitivity and high S/N ratio, excellent light fastness and property for repeating use, high image density and clear half tone and can provide high quality image with high resolution power repeatingly.
  • the amorphous material constituting the light receiving layer in this invention is prepared by vacuum depositing method utilizing the discharging phenomena such as glow discharging, sputtering, and ion plating process. These production processes are properly used selectively depending on the factors such as the manufacturing conditions, the installation cost required, producting scale and properties required for the light receiving members to be prepared.
  • the glow discharging process or sputtering process is suitable since the control for the condition upon preparing the light receiving members having desired properties are relatively easy and carbon atoms and hydrogen atoms can be introduced easily together with silicon atoms.
  • the glow discharging process and the sputtering process may be used together in one identical system.
  • a layer constituted with a-Si(H,X) is formed, for example, by the glow discharging process, gaseous starting material for supplying Si capable of supplying silicon atoms(Si) are introduced together with gaseous starting material for introducing hydrogen atoms(H) and/or halogen atoms(X) into a deposition chamber the inside pressure of which can be reduced, glow discharge is generated in the deposition chamber, and a layer composed of a-Si(H, X) is formed on the surface of a predetermined support disposed previously at a predetermined position.
  • the gaseous starting material for supplying Si can include gaseous or gasifiable silicon hydrides (silanes) such as SiH 4 , Si 2 H s , Si 3 H 8 , Si 4 H, o , etc., SiH 4 and Si 2 H s being particularly preferred in view of the easy layer forming work and the good efficiency for the supply of Si.
  • silanes gaseous or gasifiable silicon hydrides
  • halogen compounds can be mentioned as the gaseous starting material for introducing the halogen atoms and gaseous or gasifiable halogen compounds, for example, gaseous halogen, halides, inter-halogen compounds and halogen-substituted silane derivatives are preferred.
  • gaseous halogen, halides, inter-halogen compounds and halogen-substituted silane derivatives are preferred.
  • they can include halogen gas such as of fluorine, chlorine, bromine, and iodine; inter-halogen compounds such as BrV, CIF, CIF 3 , BrF 2 , BrF 3 , IF 7 , ICI, IBr, etc.; and silicon halides such as SiF 4 , Si 2 F 6 , SiC1 4 , and SiBr 4 .
  • the use of the gaseous or gasifiable silicon halide as described above is particularly advantageous since the layer constituted with halogen atom-containing a-Si can
  • the gaseous starting material usable for supplying hydrogen atoms can include those gaseous or gasifiable materials, for example, hydrogen gas, halides such as HF, HCI, HBr, and HI, silicon hydrides such as SiH 4 , Si 2 H 6 , Si 3 H 8 , and Si 4 H, o , or halogen-substituted silicon hydrides such as SiH 2 F 2 , SiH 2 1 2 , SiH 2 CI 2 , SiHCI 3 , SiH 2 Br 2 , and SiHBr 3 .
  • the use of these gaseous starting material is advantageous since the content of the hydrogen atoms(H), which are extremely effective in view of the control for the electrical or photoelectronic properties, can be controlled with ease.
  • the use of the hydrogen halide or the halogen-substituted silicon hydride as described above is particularly advantageous since the hydrogen atoms(H) are also introduced together with the introduction of the halogen atoms.
  • the halogen atoms are introduced by introducing gaseous halogen compounds or halogen atom-containing silicon compounds into a deposition chamber thereby forming a plasma atmosphere with the gas.
  • the gaseous starting material for introducing the hydrogen atoms for example, H 2 or gaseous silanes are described above are introduced into the sputtering deposition chamber thereby forming a plasma atmosphere with the gas.
  • a layer comprising a-Si(H, X) is formed on the support by using an Si target and by introducing a halogen atom-introducing gas and H 2 gas together with an inert gas such as He or Ar as required into a deposition chamber thereby forming a plasma atmosphere and then sputtering the Si target.
  • a feed gas to liberate silicon atoms(Si), a feed gas to liberate germanium atoms, and a feed gas to liberate hydrogen atoms(H) and/or halogen atoms(X) are introduced into an evacuatable deposition chamber, in which the glow discharge is generated so that a layer of A-SiGe(H, X) is formed on the properly positioned support.
  • the feed gases to supply silicon atoms, halogen atoms, and hydrogen atoms are the same as those used to form the layer of a-Si(H, X) mentioned above.
  • the feed gas to liberate Ge includes gaseous or gasifiable germanium halides such as GeH 4 , Ge 2 H 6 , Ge 3 H 8 , Ge 4 H 10 , Ge 5 H 12 , Ge 6 H 14 , Ge 7 H 16 , Ge 8 H 18 , and Ge 9 H 2 o, with GeH 4 , Ge 2 H 6 , and Ge 3 H 8 , being preferable on account of their ease of handling and the effective liberation of germanium atoms.
  • a-SiGe(H, X) by the sputtering process, two targets (a silicon target and a germanium target) or a single target composed of silicon and germanium is subjected to sputtering in a desired gas atmosphere.
  • the vapors of silicon and germanium are allowed to pass through a desired gas plasma atmosphere.
  • the silicon vapor is produced by heating polycrystal silicon or single crystal silicon held in a boat
  • the germanium vapor is produced by heating polycrystal germanium or single crystal germanium held in a boat. The heating is accomplished by resistance heating or electron beam method (E.B. method).
  • the layer may be incorporated with halogen atoms by introducing one of the above-mentioned gaseous halides or halogen-containing silicon compounds into the deposition chamber in which a plasma atmosphere of the gas is produced.
  • a feed gas to liberate hydrogen is introduced into the deposition chamber in which a plasma atmosphere of the gas is produced.
  • the feed gas may be gaseous hydrogen, silanes, and/or germanium hydrides.
  • the feed gas to liberate halogen atoms includes the above-mentioned halogen-containing silicon compounds.
  • feed gas examples include hydrogen halides such as HF, HCI, HBr, and HI; halogen-substituted silanes such as SiH 2 F 2 , SiH 2 l 2 , SiH 2 Cl 2 , SiHCl 3 , SiH 2 Br 2 , and SiHBr 3 ; germanium hydride halide such as GeHF 3 , GeH 2 F 2 , GeH 3 F, GeHCl 3 , GeH 2 CI 2 , GeH 3 Cl, GeHBr 3 , GeH 2 Br 2 , GeH 3 Br, GeHI 3 , GeH 2 1 2 , and GeH 3 1; and germanium halides such as GeF4, GeCl 4 , GeBr 4 , Gel 4 , GeF 2 , GeCl 2 , GeCl 2 , GeBr 2 , and Gel 2 . They are in the gaseous form or gasifiable substances.
  • halogen-substituted silanes such as SiH 2 F 2
  • a starting material (feed gas) to release tin atoms(Sn) is used in place of the starting material to release germanium atoms which is used to form the layer composed of a-SiGe(H, X) as mentioned above.
  • the process is properly controlled so that the layer contains a desired amount of tin atoms.
  • Examples of the feed gas to release tin atoms (Sn) include tin hydride (SnH 4 ) and tin halides (such as SnF 2 , SnF 4 , SnCl 2 , SnCl 4 , SnBr 2 , SnBr 4 , Snl 2 , and Snl 4 ) which are in the gaseous form or gasifiable.
  • Tin halides are preferable because they form on the substrate a layer of a-Si containing halogen atoms.
  • SnC1 4 is particularly preferable because of its ease of handling and its efficient tine supply.
  • solid SnC1 4 is used as a starting material to supply tin atoms (Sn), it should preferably be gasified by blowing (bubbling) an inert gas (e.g., Ar and He) into it while heating.
  • an inert gas e.g., Ar and He
  • the gas thus generated is introduced, at a desired pressure, into the evacuated deposition chamber.
  • the layer may be formed from an amorphous material (a-Si(H, X) or a-Si(Ge, Sn)H, X)) which further contains the group III atoms or group V atoms, nitrogen atoms, oxygen atoms, or carbon atoms, by the glow-discharge process, sputtering process, or ion-plating process.
  • a-Si(H, X) or a-Si(Ge, Sn)(H, X) is used in combination with the starting materials to introduce the group III atoms or group V atoms, nitrogen atoms, oxygen atoms, or carbon atoms.
  • the supply of the starting materials should be properly controlled so that the layer contains a desired amount of the necessary atoms.
  • the layer is to be formed by the glow-discharge process from a-Si(H, X) containing atoms (O, C, N) or from a-Si(Ge, Sn)(H, X) containing atoms (O, C, N)
  • the starting material to form the layer of a-Si(H, X) or a-Si(Ge, Sn)(H, X) should be combined with the starting material used to introduce atoms (0, C, N).
  • the supply of these starting materials should be properly controlled so that the layer contains a desired amount of the necessary atoms.
  • the starting material to introduce the atoms (O, C, N) may be any gaseous substance or gasifiable substance composed of any of oxygen, carbon, and nitrogen.
  • Examples of the starting materials used to introduce oxygen atoms (O) include oxygen (0 2 ), ozone (0 3 ), nitrogen dioxide (N0 2 ), nitrous oxide (N 2 0), dinitrogen trioxide (N 2 0 3 ), dinitrogen tetroxide (N 2 0 4 ), dinitrogen pentoxide (N 2 0 5 ), and nitrogen trioxide (N0 3 ).
  • Additional examples include lower siloxanes such as disiloxane (H 3 SiOSiH 3 ) and trisiloxane (H 3 SiOSiH 2 OSiH 3 ) which are composed of silicon atoms (Si), oxygen atoms (0), and hydrogen atoms (H).
  • lower siloxanes such as disiloxane (H 3 SiOSiH 3 ) and trisiloxane (H 3 SiOSiH 2 OSiH 3 ) which are composed of silicon atoms (Si), oxygen atoms (0), and hydrogen atoms (H).
  • Examples of the starting materials used to introduce carbon atoms include saturated hydrocarbons having 1 to 5 carbon atoms such as methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ), n-butane (n-C 4 H 1o ), and pentane (C 5 H 12 ); ethyleneic hydrocarbons having 2 to 5 carbon atoms such as ethylene (C 2 H 4 ), propylene (C 3 H 6 ), butene-1 (C 4 H 8 ), butene-2 (C 4 H 8 ), isobutylene (C 4 H 8 ), and pentene (C 5 H 10 ); and acetylenic hydrocarbons having 2 to 4 carbon atoms such as acetylene (C 2 H 2 ), methyl acetylene (C 3 H 4 ), and butine (C 4 H 6 ).
  • saturated hydrocarbons having 1 to 5 carbon atoms such as methane (CH 4 ), ethane (C 2 H 6 ), propane
  • Examples of the starting materials used to introduce nitrogen atoms include nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (H 2 NNH 2 ), hydrogen azide (HN 3 ), ammonium azide (NH 4 N 3 ), nitrogen trifluoride (F 3 N), and nitrogen tetrafluoride (F 4 N).
  • the starting material for introducing the group III or group V atoms are used together with the starting material for forming a-Si (H, X) or a-Si (Ge, Sn) (H, X) upon forming the layer constituted with a-Si (H, X) or a-Si (Ge, Sn) (H, X) as described above and they are incorporated while controlling the amount of them into the layer to be formed.
  • the boron atom introducing materials as the starting material for introducing the group III atoms, they can include boron hydrides such as B 2 H 6 , B 4 H 10' BH9, B 5 H 11 , B 6 H 10 , and BsH, 4 , and boron halides such as BF 3 , BCI 3 , and BBr 3 .
  • boron hydrides such as B 2 H 6 , B 4 H 10' BH9, B 5 H 11 , B 6 H 10 , and BsH, 4
  • boron halides such as BF 3 , BCI 3 , and BBr 3 .
  • AICI 3 , CaCl 3 , Ga(CH 3 ) 2 , InCI 3 , TICI 3 , and the like can also be mentioned.
  • the starting material for introducing the group V atoms and, specifically, to the phosphorous atom introducing materials can include, for example, phosphorus halides such as PH 3 and P 2 H 6 and phosphous halides such as PH 4 1, PF 3 , PF s , PCI 3 , PCl 5 , PBr 3 , PBR 3 , and P1 3 .
  • AsH 3 , AsF s , AsC1 3 , AsBr 3 , AsF 3 , SbH 3 , SbF 3 , SbF s , SbC1 3 , SbCl 5 , BiH 3 , BiCI 3 , and BiBr 3 can also be mentioned to as the effective starting material for introducing the group V atoms.
  • the light receiving layer of the light receiving member of this invention is produced by the glow discharge process or sputtering process.
  • the amount of germanium atoms and/or tin atoms; the group III atoms or group V atoms; oxygen atoms, carbon atoms, or nitrogen atoms; and hydrogen atoms and/or halogen atoms in the light receiving layer is controlled by regulating the flow rate of the starting materials entering the deposition chamber.
  • the conditions upon forming the light receiving layer of the light receiving member of the invention for example, the temperature of the support, the gas pressure in the deposition chamber, and the electric discharging power are important factors for obtaining the light receiving member having desired properties and they are properly selected while considering the functions of the layer to be made. Further, since these layer forming conditions may be varied depending on the kind and the amount of each of the atoms contained in the light receiving layer, the conditions have to be determined also taking the kind or the amount of the atoms to be contained into consideration.
  • the temperature of the support is usually from 50 to 350°C and, more preferably, from 50 to 250°C; the gas pressure in the deposition chamber is usually from 0.01 to 1 Torr and, particularly preferably, from 0.1 to 0.5 Torr; and the electrical discharging power is usually from 0.005 to 50 W/cm 2 , more preferably, from 0.01 to 30 W/cm 2 and, particularly preferably, from 0.01 to 20 W/cm 2 .
  • the temperature of the support is usually from 50 to 350°C, preferably, from 50 to 300°C, most suitably 100 to 300°C;
  • the gas pressure in the deposition chamber is usually from 0.01 to 5 Torr, preferably, from 0.001 to 3 Torr, most suitably from 0.1 to 1 Torr;
  • the electrical discharging power is usually from 0.005 to 50 W/cm 2 , preferably, from 0.01 to 30 W/cm 2 , most preferably, from 0.01 to 20 W/cm 2 .
  • the actual conditions for forming the layer such as temperature of the support, discharging power and the gas pressure in the deposition chamber cannot usually be determined with ease independent of each other. Accordingly, the conditions optimal to the layer formation are desirably determined based on relative and organic relationships for forming the amorphous material layer having desired properties.
  • the layer is formed, for example, in the case of the glow discharging process, by properly varying the gas flow rate of gaseous starting material for introducing germanium atoms and/or tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, or the group III atoms or group V atoms upon introducing into the deposition chamber in accordance with a desired variation coefficient while maintaining other conditions constant.
  • the gas flow rate may be varied, specifically, by gradually changing the opening degree of a predetermined needle valve disposed to the midway of the gas flow system, for example, manually or any of other means usually employed such as in externally driving motor.
  • the variation of the flow rate may not necessarily be linear by a desired content curve may be obtained, for example, by controlling the flow rate along with a previously designed variation coefficient curve by using a microcomputer or the like.
  • a desired distributed state of the germanium atoms and/or tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, or the group III atoms or group V atoms in the direction of the layer thickness may be formed with the distribution density being varied in the direction of the layer thickness by using gaseous starting material for introducing the germanium atoms and/or tin atoms, oxygen atoms, carbon atoms, nitrogen atoms, or the group III atoms or group V atoms and varying the gas flow rate upon introducing these gases into the deposition chamber in accordance with a desired variation coefficient in the same manner as the case of using the glow discharging process.
  • the layer thickness In the case of the light receiving layer having the surface layer composed of at least one kind selected from inorganic fluorides, inorganic oxides, and inorganic sulfides, it is necessary to control the layer thickness at an optical level in order to effectively achieve the object of the invention. To this end, vapor deposition, sputtering, gas phase plasma, optical CVD, heat CVD, or the like may be used. These forming processes are, of course, properly selected while considering those factors such as the kind of the forming materials for the surface layer, production conditions, installation cost required, and production scale.
  • the sputtering process may preferably be employed in the case of using the inorganic compounds for forming the surface layer. That is, the inorganic compound for forming the surface layer is used as a target and Ar gas is used as a sputtering gas, and the surface layer is deposited on the support, on which the light receiving layer made of amorphous material has previously been formed, by causing glow discharging and sputtering the inorganic compounds.
  • the light receiving layer composed of an amorphous material was formed by using the glow discharging process and the surface layer composed of an inorganic compound was formed by using the sputtering process.
  • Figure 25 shows the apparatus for preparing the light receiving member according to this invention.
  • Gas cylinders 2502, 2503, 2504, 2505, and 2506 illustrated in the figure are charged with gaseous starting materials for forming the respective layers in this invention, that is, for instance, SiF 4 gas (99.999% purity) in gas cylinder 2505 B 2 H 6 gas (99.999% purity) diluted with H 2 (referrred to as B 2 H 6 /H 2 ) in gas cylinder 2503, CH 4 gas (99.999% purity) in gas cylinder 2504, GeF 4 gas (99.999% purity) in gas cylinder 2505, and inert gas (He) in gas cylinder 2506'. SnC1 4 is held in a closed container 2506'.
  • valves 2522-2526 for the gas cylinders 2502-2506 and a leak valve 2535 are closed and that inlet valves 2512-2516, exit valves 2517-2521, and sub-valves 2532 and 2533 are opened.
  • a main valve 2534 is at first opened to evacuate the inside of the reaction chamber 2501 and gas piping.
  • SiH 4 gas from the gas cylinder 2502, B 2 H 6 /H 2 gas from the gas cylinder 2503, CH 4 gas from the gas cylinder 2504, and GeF 4 gas from the gas cylinder 2505 are caused to flow into mass flow controllers 2507, 2508, 2509, and 2510 respectively by opening the inlet valves 2512, 2513, 2514, and 2515, controlling the pressure of exit pressure gauges 2527, 2528, 2529, and 2530 to 1 kg/cm 2 .
  • the exit valves 2517, 2518, 2519, and 2520, and the sub-valve 2532 are gradually opened to enter the gases into the reaction chamber 2501.
  • the exit valves 2517, 2518, 2519, and 2520 are adjusted so as to attain a desired value for the ratio among the SiF 4 gas flow rate, GeF 4 gas flow rate, CH 4 gas flow rate, and B 2 H 6 /H 2 gas flow rate, and the opening of the main valve 2534 is adjusted while observing the reading on the vacuum gauge 2536 so as to obtain a desired value for the pressure inside the reaction chamber 2501.
  • a power source 2450 is set to a predetermined electrical power to cause glow discharging in the reaction chamber 2501 while controlling the flow rates of SiF 4 gas, GeF 4 gas, CH 4 gas, and B 2 H 4 /H 2 gas in accordance with a previously designed variation coefficient curve by using a microcomputer (not shown), thereby forming, at first, a layer 102' containing silicon atoms, germanium atoms, carbon atoms, and boron atoms on the substrate cylinder 2537.
  • the exit valves 2518 and 2520 are completely closed, and the glow discharge is continued in the same manner except that the discharge conditions are changed as required, whereby a layer 102" containing substantially no germanium atoms is formed on the layer 102'.
  • the light receiving layer is incorporated with tin atoms and SnCl 4 is used as the feed gas (starting material for tin atoms
  • solid SnC1 4 placed in 2506' is heated by a heating means (not shown) and an inert gas such as He is blown for bubbling from the inert gas cylinder 2506.
  • the thus generated gas of SnC1 4 is introduced into the reaction chamber in the same manner as mentioned for SiF 4 gas, GeF 4 gas, CH 4 gas, and B 2 H 6 /H 2 gas.
  • the valve for the feed gases and diluent gas used for the layer of amorphous material are closed, and then the leak valve 2535 is gradually opened so that the pressure in the deposition chamber is restored to the atmospheric pressure and the deposition chamber is scavenged with argon gas.
  • a target of inorganic compound for the formation of the surface layer is spread all over the cathode (not shown), and the deprotection chamber is evacuated, with the leak valve 2535 closed, and argon gas is introduced into the deposition chamber until a pressure of 0.015 to 0.02 Torr is reached.
  • a high-frequency power 150 to 170 W is applied to bring about glow discharge, whereby sputtering the inorganic compound so that the surface layer is deposited on the previously formed layer.
  • Rigid spheres of 0.6 mm diameter made of SUS stainless steels were chemically etched to form an unevenness to the surface of each of the rigid spheres.
  • etching agent Usable as the etching agent are an acid such as hydrochloric acid, hydrofluoric acid, sulfuric acid and chromic acid and an alkali such as caustic soda.
  • an aqueous solution prepared by admixing 1.0 volumetric part of concentrated hydrochloric acid to 1.0 to 4.0 volumetric part of distilled water was used, and the period of time for the rigid spheres to be immersed in the aqueous solution, the acid concentration of the aqueous solution and other necessary conditions were appropriately adjusted to form a desired unevenness to the surface of each of the rigid spheres.
  • the radius of curvature R and the width D of the dimple was determined depending on the conditions such as the diameter R' for the rigid sphere, the falling height h and the like. It was also confirmed that the pitch between each of the dimples (density of the dimples or the pitch for the uneveness) could be adjusted to a desired pitch by controlling the rotating speed or the rotation number of the cylinder, or the falling amount of the rigid sphere.
  • R the magnitude of R and of D
  • R it is not preferred for R to be less than 0.1 mm because of the rigid spheres to be employed in that case are to be lighter and smaller, that results in making it difficult to control the formation of the dimples as expected.
  • R it is not preferred for R to be more than 2.0 mm because the rigid spheres to be employed in that case are to be heavier and the falling height is to be extremely lower, for instance, in the case where D is desired to be relatively smaller in order to adjust the falling height, that results in making it also difficult to control the formation of the dimples as expected.
  • D is not preferred for D to be less than 0.02 mm because the rigid spheres to be employed in that case are to be of a smaller size and to be lighter in order to secure their falling height, that results in making it also difficult to control the formation of the dimples as expected.
  • These light receiving members were subjected to imagewise exposure by irradiating laser beams at 780 nm wavelength and with 80 pm spot diameter using an image exposing device shown in Figure 26 and images were obtained by subsequent development and transfer.
  • the state of the occurrence of interference fringe on the thus obtained images were as shown in the lower row of Table 1A.
  • Figure 26(A) is a schematic plan view illustrating the entire exposing device
  • Figure 26(B) is a schematic side elevational view for the entire device.
  • a light receiving member 2601 is shown in the figures, and a semiconductor laser 2602, and f ⁇ lens 2603, and a polygonal mirror 2604.
  • a light receiving member was manufactured in the same manner as described above by using an aluminium alloy cylinder, the surface of which was fabricated with a conventional cutting tool (60 mm in diameter, 298 mm in length, 100 ⁇ m uneveness pitch, and 3 pm uneveness depth).
  • a conventional cutting tool 60 mm in diameter, 298 mm in length, 100 ⁇ m uneveness pitch, and 3 pm uneveness depth.
  • a light receiving layer was formed on AI supports (cylinder Nos. 101 to 107) in the same manner as in Example 1 except for forming these light receiving layers in accordance with the layer forming conditions shown in Table 2B. Incidentally, while the light receiving layer was formed, the flow rates of SiF 4 and GeF 4 were controlled automatically using a microcomputer according to the flow rate curve as shown in Figure 27.
  • a light receiving layer was formed on an AI support (Sample Nos. 103 to 106) in the same manner as in Example 1 except for forming these light receiving layers in accordance with the layer forming conditions shown in Tables 3 through 11.
  • the flow rates for the gases used upon forming the light receiving layers were automatically adjusted under the microcomputer control in accordance with the flow rate variation curves shown in Figures 28 through 36, respectively.
  • the boron atoms were incorporated so that their concentration in the entire layer is about 200 ppm.
  • a light receiving layer was formed on an AI support (Sample Nos. 103 to 106) in the same manner as in Example 1 except for forming these light receiving layers in accordance with the layer forming conditions shown in Tables 12 through 21.
  • the flow rates for the gases used upon forming the light receiving layers were automatically adjusted under the microcomputer control in accordance with the flow rate variation curves shown in Figures 37 through 45, respectively.
  • the boron atoms were incorporated so that their concentration in the entire layer is about 200 ppm.
  • Light receiving members were prepared on AI supports (cylinder Nos. 103 to 106) of Example 1 in the same manner as in Example 1 except for forming these light receiving members in accordance with the layer forming conditions shown in Tables 22 through 32.
  • the flow rates for the gases used in the first and second steps upon forming the light receiving layers were automatically adjusted under the microcomputer control in accordance with the flow rate variation curves shown in Figures 27 through 36, respectively.
  • Light receiving members were prepared on AI supports (cylinder Nos. 103 to 106) of Example 1 in the same manner as in Example 1 except for forming these light receiving members in accordance with the layer forming conditions shown in Tables 33 through 43.
  • the flow rates for the gases used in the first and second steps upon forming the light receiving layers were automatically adjusted under the microcomputer control in accordance with the flow rate variation curves shown in Figures 37 through 39, 46, and 40 through 45, respectively.
  • the boron atoms were incorporated so that their concentration in the entire layer is about 200 ppm.
  • a light receiving layer was formed on an A1 support (cylinder No. 105) of Example 1 in accordance with the layer forming conditions shown in Table 44A. Boron atoms were incorporated under the same conditions as in Example 5. The flow rates of GeH 4 gas, SiH 4 gas, H 2 gas, and NH 3 gas at the time of forming the light receiving layer were automatically adjusted under the microcomputer control in accordance with the flow rate variation curves shown in Figure 38.
  • the surface layer was formed by the sputtering process.
  • the material used for forming each of the surface layer is shown in the upper row of Table 44B.
  • the thickness of the surface layer is shown in the lower row of Table 44B.
  • a light receiving layer was formed on an A1 support (cylinder No. 105) in the same manner as in Example 44 in accordance with the layer forming conditions shown in Table 45.
  • the flow rates of GeF 4 gas and SiF 4 gas at the time of forming the light receiving layer were automatically adjusted under the microcomputer control in accordance with the flow rate variation curve shown in Figures 39.
  • the surface layer (1-20) was formed in the same manner as in Example 44.
  • a light receiving layer was formed on an A1 support (cylinder Nos. 103-106) of Example 1 in accordance with the layer forming conditions shown in Tables 46 through 54.
  • a surface layer was formed on the light receiving layer by the sputtering process. The composition of the surface layer is shown in the upper row of Table 55 and the thickness of the surface layer is shown in the lower row of Table 55.
  • the concentration of boron atoms in the layer was 200 ppm in each example.

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Claims (18)

1. Lichtempfangendes Element, das für die Erzeugung eines Bilds zu belichten ist, wobei das Element einen Träger und eine darauf gebildete lichtempfangende Schicht mit Mehrschichtenstrucktur aufweist, wobei die lichtempfangende Schicht eine innere photoempfindliche Schicht, die aus einem amorphen Material besteht, das Siliciumatome und wenigstens entweder Germaniumatome oder Zinnatome, enthält, und eine äußere photoempfindliche Schicht, die aus einem amorphen Material besteht, das Siliciumatome und weder Germaniumatome noch Zinnatome enthält, umfaßt, wobei der Träger eine Oberfläche hat, die eine Vielzahl von kugelförmigen Vertiefungen aufweist, die derart über die Oberfläche verteilt sind, daß sich ihre Peripherien berühren, wobei der Krümmungsradius R und die Breite D der kugelförmigen Vertiefungen Werte haben, die dem Kriterium: 0,035 Z D/R Z 0,5 genügen, wobei D Z 0,5 mm, und jede der Vertiefungen eine Innenfläche hat, die sehr kleine Unregelmäßigkeiten aufweist, wobei jede Unregelmäßigkeit eine Höhe h hat, die dem folgenden Kriterium genügt: 0,5 pm Z h ≦ 20 pm.
2. Lichtempfangendes Element nach Anspruch 1, bei dem die kugelförmigen Vertiefungen denselben Krümmungsradius haben.
3. Lichtempfangendes Element nach Anspruch 1, bei dem die kugelförmigen Vertiefungen denselben Krümmungsradius und dieselbe Breite haben.
4. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem die kugelförmigen Vertiefungen gebildet werden, indem eine Vielzahl von starren Kugeln, von denen jede eine Oberfläche hat, die sehr kleine Unregelmäßigkeiten aufweist, spontan auf die Oberfläche des Trägers fallen gelassen werden.
5. Lichtempfangendes Element nach Anspruch 4, bei dem die kugelförmigen Vertiefungen gebildet werden, indem die Vielzahl von starren Kugeln, die fast denselben Durchmeser haben, aus fast derselben Höhe spontan auf die Oberfläche des Trägers fallen gelassen werden.
6. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem der Träger ein Metallkörper ist.
7. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem die lichtempfangende Schicht eine Substanz für die Steuerung der Leitfähigkeit enthält.
8. Lichtempfangendes Element nach einem der vorhergehenden Anspruche, bei dem die lichtempfangende Schicht als eine der Schichten, die sie bilden, eine zur Verhinderung von Landungsinjektion dienende Schicht hat, die eine Substanz für die Steuerung der Leitfähigkeit enthält.
9. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem die lichtempfangende Schicht als eine der Schichten, die sie bilden, eine Sperrschicht hat.
10. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem die lichtempfangende Schicht wenigstens eine Atomart enthält, die aus Sauerstoffatomen, Kohlenstoffatomen und Stickstoffatomen ausgewählt ist.
11. Lichtempfangendes Element nach einem der vorhergehenden Ansprüche, bei dem die lichtempfangende Schicht als eine der Schichten, die sie bilden, eine Oberflächenschicht hat.
12. Lichtempfangendes Element nach Anspruch 11, bei dem die Oberflächenschicht aus einem amorphen Material hergestellt ist, das aus Siliciumatomen und einer Atomart besteht, die aus Sauerstoffatomen, Kohlenstoffatomen und Stickstoffatomen ausgewählt ist, wobei die eine Atomart von der Atomart, die in der lichtempfangenden Schicht enthalten ist, verschieden ist.
13. Lichtempfangendes Element nach Anspruch 12, bei dem die Oberflächenschicht gleichmäßig wenigstens eine Atomart enthält, die aus Sauerstoffatomen, Kohlenstoffatomen und Stickstoffatomen ausgewählt ist.
14. Lichtempfangendes Element nach Anspruch 11, bei dem die Oberflächenschicht aus einem Material besteht, das die Funktion der Verhinderung von Reflexion hat.
15. Lichtempfangendes Element nach Anspruch 13, bei dem die Oberflächenschicht aus wenigstens einer Art besteht, die aus anorganischen Fluoriden, anorganischen Oxiden und anorganischen Sulfiden ausgewählt ist.
16. Lichtempfangendes Element nach Anspruch 14, bei dem die Oberflächenschicht eine Dicke d hat, die durch die folgende Gleichung definiert ist:
Figure imgb0065
worin A die Wellenlänge des einfallenden Lichtes ist, mit dem das lichtempfangende Element abgetastet werden soll, n der Brechungsindex der die Oberflächenschicht bildenden Substanz ist und m eine positive ungerade Zahl ist.
17. Lichtempfangendes Element nach Anspruch 14, bei dem die Oberflächenschicht aus einer Substanz besteht, die einen Brechungsindex n hat, und die lichtempfangende Schicht, die an die Oberflächenschicht angrenzt, aus einer amorphen Substanz besteht, die einen Brechungsindex na hat, wobei n und n8 die folgende Gleichung erfüllen:
Figure imgb0066
18. Elektrophotographisches Verfahren, bei dem
(a) das lichtempfangende Element nach einem der Ansprüche 1 bis 17 mit Information tragenden elektromagnetischen Wellen bildmäßig bestrahlt wird, um dadurch ein elektrostatisches Bild (Ladungsbild) zu erzeugen, und
(b) das elektrostatische Bild entwickelt wird.
EP86308376A 1985-10-28 1986-10-28 Lichtempfindliche Elemente Expired - Lifetime EP0223448B1 (de)

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4798776A (en) * 1985-09-21 1989-01-17 Canon Kabushiki Kaisha Light receiving members with spherically dimpled support
US4808504A (en) * 1985-09-25 1989-02-28 Canon Kabushiki Kaisha Light receiving members with spherically dimpled support
JPS6290663A (ja) * 1985-10-17 1987-04-25 Canon Inc 光受容部材
CA1289404C (en) * 1985-10-24 1991-09-24 Keiichi Murai Electrophotographic light receiving members comprising amorphous silicon and substrate having minute irregularities
JPH10186102A (ja) * 1996-12-26 1998-07-14 Yazaki Corp 反射防止膜
US7928317B2 (en) 2006-06-05 2011-04-19 Translucent, Inc. Thin film solar cell
US8071872B2 (en) 2007-06-15 2011-12-06 Translucent Inc. Thin film semi-conductor-on-glass solar cell devices
US8542437B1 (en) 2010-03-09 2013-09-24 Translucent, Inc. Earth abundant photonic structures
KR101300035B1 (ko) 2010-05-05 2013-08-29 엘지디스플레이 주식회사 반사형 및 반사투과형 액정표시장치용 어레이 기판 및 그 제조방법
WO2019187078A1 (ja) * 2018-03-30 2019-10-03 シャープ株式会社 表示デバイスの製造方法

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599542A (en) * 1948-03-23 1952-06-10 Chester F Carlson Electrophotographic plate
FR1346711A (fr) * 1962-02-08 1963-12-20 Kalle Ag Matériel électrophotographique
JPS4913325B1 (de) * 1970-05-02 1974-03-30
US3743847A (en) * 1971-06-01 1973-07-03 Motorola Inc Amorphous silicon film as a uv filter
CH589306A5 (de) * 1975-06-27 1977-06-30 Bbc Brown Boveri & Cie
GB1588370A (en) * 1978-05-11 1981-04-23 Standard Telephones Cables Ltd Infra-red transmitting elements
JPS55137536A (en) * 1979-04-13 1980-10-27 Fuji Photo Film Co Ltd Transfer film for electrophotographic copier
JPS55144251A (en) * 1979-04-27 1980-11-11 Ricoh Co Ltd Electrophotographic receptor having selenium type photoconductive layer with roughened surface and its preparation
DE3204221A1 (de) * 1982-02-08 1983-08-18 Hoechst Ag, 6230 Frankfurt Elektrophotographisches aufzeichnungsverfahren und hierfuer geeignete photoleiterschicht
JPS58162975A (ja) * 1982-03-24 1983-09-27 Canon Inc 電子写真感光体
FR2524661B1 (fr) * 1982-03-31 1987-04-17 Canon Kk Element photoconducteur
US4419397A (en) * 1982-04-14 1983-12-06 Neat Clarence E Scabrous surface light director
US4514582A (en) * 1982-09-17 1985-04-30 Exxon Research And Engineering Co. Optical absorption enhancement in amorphous silicon deposited on rough substrate
US4663188A (en) * 1982-09-27 1987-05-05 Rca Corporation Method for making a photodetector with enhanced light absorption
JPS5974567A (ja) * 1982-10-20 1984-04-27 Olympus Optical Co Ltd 電子写真感光体
US4599482A (en) * 1983-03-07 1986-07-08 Semiconductor Energy Lab. Co., Ltd. Semiconductor photoelectric conversion device and method of making the same
US4532198A (en) * 1983-05-09 1985-07-30 Canon Kabushiki Kaisha Photoconductive member
JPS6079360A (ja) * 1983-09-29 1985-05-07 Kyocera Corp 電子写真感光体及びその製造方法
US4511614A (en) * 1983-10-31 1985-04-16 Ball Corporation Substrate having high absorptance and emittance black electroless nickel coating and a process for producing the same
JPS60166956A (ja) * 1984-02-09 1985-08-30 Canon Inc 感光体及びそれを用いた画像形成方法
US4650736A (en) * 1984-02-13 1987-03-17 Canon Kabushiki Kaisha Light receiving member having photosensitive layer with non-parallel interfaces
US4705732A (en) * 1984-04-27 1987-11-10 Canon Kabushiki Kaisha Member having substrate with projecting portions at surface and light receiving layer of amorphous silicon
US4696881A (en) * 1984-07-10 1987-09-29 Canon Kabushiki Kaisha Member having light receiving layer with smoothly connected interfaces
US4683160A (en) * 1985-05-09 1987-07-28 Exxon Research And Engineering Company Solar cells with correlated roughness substrate
CA1289404C (en) * 1985-10-24 1991-09-24 Keiichi Murai Electrophotographic light receiving members comprising amorphous silicon and substrate having minute irregularities
JPS62106470A (ja) * 1985-11-02 1987-05-16 Canon Inc 光受容部材
EP0570826A1 (de) * 1992-05-20 1993-11-24 Akzo Nobel N.V. Celluloseacetatmembranen

Also Published As

Publication number Publication date
AU6441986A (en) 1987-04-30
CA1288271C (en) 1991-09-03
DE3676957D1 (de) 1991-02-21
US4834501A (en) 1989-05-30
EP0223448A3 (en) 1987-08-26
EP0223448A2 (de) 1987-05-27
AU581543B2 (en) 1989-02-23

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